EP3625320A1 - Composition - Google Patents

Abstract

An aqueous detergent liquid composition comprising: (i) a surfactant system comprising anionic surfactant, and (ii) at least 0.05 wt % of a polymer formed from the polymerisation of monomers consisting of monomer (A1): R¹C=CR²R³ (A1) And optionally monomer (A2): R⁴C=CR⁵R⁶ (A2) R¹ and R² are each independently selected from H, methyl, -C(=O)OH, or -C(=O)OR⁷, wherein R⁷ is a C₁-C₃₀ alkyl; R³ is T¹-[CH₂]_k-[O]_p-[R⁸O]_q-Y¹-R⁹ T¹ is -CH₂C(=O)O-, -C(=O)O-, -O-, -CH₂O-, -NHC(=O)NH-, -C(=O)NH-, -Ar-(CE₂)_x-NHC(=O)O-, -Ar-(CE₂)_x-NHC(=O)NH-, or -CH₂CH₂NHC(=O)-; Ar is divalent aryl; E is H or methyl; x is 0 or 1; k is an integer in the range of 0 to 30; and p is 0 or 1; optionally with the proviso that when k is 0, p is 0, and when k is in the range of 1 to 30; p is 1; (R⁸O)_q is polyoxyalkylene, which is a homopolymer, a random copolymer, or a block copolymer of C₂-C₄-oxyalkylene units, wherein R⁸ is C₂H₄, C₃H₆, C₄H₈, or a mixture thereof, and n is an integer in the range of 5 to 250; Y¹ is -R⁸O-, -R⁸H-, -C(=O)-, -C(=O)NH-, =R⁸NHC(=O)NH-, or - C(=O)NHC(=O)-; and R⁹ is substituted or unsubstituted alkyl selected from the group consisting of C₈-C₄₀ linear alkyl, C₈-C₄₀ branched alkyl, C₈-C₄₀ carbocyclic alkyl, C₂-C₄₀ alkyl-substituted, phenyl, aryl-substituted C₂-C₄₀ alkyl, and C₈-C₈₀ complex ester; wherein the R¹¹ alkyl group optionally comprises one or more substituents selected from the group consisting of hydroxy, alkoxy, and halogen; R⁴ and R⁵ are independently H or C_1-4 alkyl, preferably H or methyl; R⁶ is -C(O)-OR¹⁰, where R¹⁰ is H or C_1-4 alkyl, preferably H or methyl, more preferably H; and wherein the degree of polymerisation of polymer (ii) is 30 or more.

Description

COMPOSITION

Technical Field

This invention relates to aqueous detergent compositions including a rheology modifying polymer useful for home care applications, including hand dish wash and laundry.

Background

A trend in detergent formulating is to reduce the amount of surfactant and to replace these petrochemical derived ingredients with highly weight efficient ingredients selected from cleaning and soil release polymers, sequestrants and enzyme cocktails. Typically some surfactant is retained in the composition and the work horse surfactant linear alkyl benzene sulphonate (LAS) is frequently a key part of the surfactant blend. The polymer ethoxylated polyethylene imine may be used as one of the weight efficient ingredients. Suitable compositions are taught, for example, in WO09153184.

It has been found that consumers prefer that the new type of concentrated liquid is thickened so that it conveys the impression of high contents when in the bottle. On the other hand, it is desirable that the pour viscosity is low enough that dosing can be done easily and accurately. A shear thinning composition is thus desired.

Hydrophobically modified alkali swellable emulsion (HASE) copolymers are a type of synthetic associative rheology modifier. This rheology modifier typically contains a backbone consisting of randomly distributed methacrylic acid (MAA) and ethylacrylate (EA) monomers, amongst other possible monomer components.

Inserted into this backbone are a small proportion of hydrophobically modified groups, usually less than 3 mol%. The monomers to form these hydrophobic groups are sometimes referred to as surfmers or associative monomers. Due to its structure, the copolymer, when dissolved in an alkaline aqueous liquid, induces a variety of interacting forces such as hydrophobic, hydrogen bonding, electrostatic, etc and this modifies the rheology of the liquid.

HASE copolymers are usually synthesized via the emulsion polymerization technique. US 5 015 71 1 (Coatex) discloses a thickening terpolymer of the MAA EA surfmer type. US 5 015 71 1 makes the following disclosure: "The first type of monomer, which is a carboxylic acid with an ethylenic unsaturation site, is a C3-C20, preferably C3-C12, compound having an ethylenic bond and at least one carboxylic group or a carboxylic acid anhydride group. The carboxylated ethylenic monomer can be selected from among monoacids, such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, cinnamic acid, diacids, such as itaconic acid, fumaric acid, maleic acid, and citraconic acid, carboxylic acid anhydrides, such as maleic anhydride and diacid hemiesters, such as the C1-4 monoesters of maleic or itaconic acids. However, the carboxyl ethylene monomer is preferably selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid".

US 4 384 096 discloses a copolymer having 42% MAA, 6% IA, 42% EA and 10% surfmer (where IA is itaconic acid). The surfmer used was Nonylphenoxy poly(ethyleneoxy)g ethyl Methacrylate. US 4 384 096 contains a general disclosure relating to the use of Itaconic acid as follows: "Acrylic or methacrylic acid or a mixture thereof with itaconic or fumaric acid are preferred, but crotonic and aconitic acid and half esters of these and other polycarboxylic acids such as maleic acid with Ci - C₄ alkanols are also suitable, particularly if used in minor amount in combination with acrylic or methacrylic acid".

Low dosage compositions formulated this way are suitable for laundry and hard surface cleaning applications. Both the removal of the surfactant and the use of cleaning polymers like ethoxylated polyethylene imine and polyester soil release polymers cause a drop in viscosity of the liquid. We have found that consumers desire that the pour viscosity of a concentrated liquid should be at least as high as a conventional dilute liquid and possibly even higher so that they have a reason to believe that the liquid contains the same cleaning power as a higher dosage detergent liquid with higher surfactant levels and possibly without such high levels of viscosity reducing polymer additives. It is also desirable to be able to include particulate materials into such liquid detergent compositions, for example encapsulated perfume or visual cues. Advantageously, the liquid should have rheology that provides a yield stress (also known as critical stress) so that the particles remain stably suspended and dispersed and yet the composition may be poured from a bottle or dispensed by a suitable spray or pump mechanism. Crosslinked hydrophobically modified copolymers are exemplified in US2004 063855 (Rohm and Haas) and where such a polymer was used at 1.5 wt% with a specified clay and 22.3 wt% mixed surfactant. It is stated that the composition synergistically increases the low shear (e. g., suspending or stabilizing) viscosity significantly while having little effect on the mid-shear (pouring) viscosity. We have found that these types of acrylates copolymers give an undesirably high pour viscosity if they are used at a high enough level to provide a suspending rheology. Alternative prior art copolymers do provide the shear thinning behaviour required for suspending but do not on their own provide the pour viscosity that is desired by consumers. This can lead to the need to use a second rheology modifying material in conjunction with the acrylate copolymer. This is an unwanted complication.

WO 2013/045377 and WO 2014/082955 describe HASE rheology modifying copolymers. WO 2013/045377 describes copolymers in slightly acidic or neutral pH compositions which exhibit high viscosity at low shear. WO 2013/045377 further makes no mention of including viscosity reducing polymers. WO 2014/082955 describes copolymers in alkaline compositions. The suspending viscosity (shear rate of 1 s^"1) is high for these polymers in simple test solution (shown in Figures 3 and 4) and the pour viscosity is suitable in a surfactant-containing composition including EPEI (shown in Tables 2 and 3).

It is an object of the present invention to provide detergent compositions with a copolymer that increases the pour viscosity while providing the required rheology for suspending, while counteracting the effect of inclusion of certain polymers that have the effect of reducing the pour viscosity of the composition. The copolymers may be utilised in compositions comprising linear alkyl benzene sulphonate anionic surfactant which is the workhorse surfactant found in most laundry and dish wash compositions.

Summary of the Invention

According to the present invention there is provided an aqueous detergent liquid composition according to claim 1 .

The polymer (ii) is a polymer formed from the polymerisation of surfactant monomer (also known as a surfmer), monomer (A1 ). In this way, polymer (ii) is either a homopolymer of monomer (A1 ) or a copolymer of monomer (A1 ) and

monomer (A2). Preferably, monomer constitutes at least 50%, more preferably at least 80%, especially preferably at least 90% and most preferably at least 95% of the total weight of the polymer.

In some embodiments, R¹ and R² are each independently selected from H and C1-3 alkyl, and R³ has the formula (VII)

-C(0)-0-[R²²0]_r-R²³ (VII)

R²² is C2-C4 and mixtures thereof, preferably C2;

r, the average number of alkoxy units R²²0, is from 6 to 40;

R²³ is alkyl or alkylaryl where the alkyl part is linear or branched; and the total number of carbons is from 8 to 40.

In some embodiments, R¹ and R² are each independently selected from H and C1-3 alkyl, and R³ has the formula (VIII)

-C(0)-0-[C2H₄0]s-CH2-(CH₂)t-CH3 (VIII)

Where s and t are independently in the range of from 6 to 40.

In some embodiments, R⁴, R⁵ and R¹⁰ are each independently H or methyl.

When monomer (A2) is present in the polymerisation to form polymer (ii) (also referred to as Polysurfmer (ii)), the molar ratio of monomer (A1 ) to monomer (A2) may be in the range of 10:90 to 90:10. In some embodiments, the molar ratio of monomer (A1 ) to monomer (A2) may be in the range of 30:70 to 70:30. In some embodiments, the polymer (ii) is formed from 50 % or more by mole of

monomer (A1 ). In preferred embodiments, the aqueous detergent liquid further includes:

(iii) at least 0.05 wt% of a copolymer formed by the addition polymerisation of:

(A) 0 to 5 wt% of a first monomer consisting of an ethylenically unsaturated diacid of formula (II): HOOC-CR¹¹=CR¹²-COOH (II) or an unsaturated cyclic anhydride precursor of such an ethylenically unsaturated diacid, the anhydride having formula (III)

where R¹¹ and R¹² are individually selected from H, C1-C3 alkyl, phenyl, chlorine and bromine;

15 to 60 wt% of a second ethylenically unsaturated monoacidic monomer consisting of (meth)acrylic acid;

30 to 70 wt% of a third ethylenically unsaturated monomer consisting of C-i-Cs alkyl ester of (meth)acrylic acid; and

1 to 25 wt% of a fourth ethylenically unsaturated monomer, consisting of surfmer of formula (IV):

R¹³-C=C-T²-[CH₂]f-[0]_g-[R¹⁶0]h-Y²-R¹⁷ (IV)

_R14 wherein each R¹³ and R¹⁴ are each independently selected from H, methyl, - C(=0)OH, or -C(=0)OR¹⁵;

R¹⁵ is a C1-C30 alkyl;

T² is -CH₂C(=0)0-, -C(=0)0-, -0-, -CH2O-, -NHC(=0)NH-, -C(=0)NH-,

-Ar-(CG₂)z-NHC(=0)0-, -Ar-(CG₂)z-NHC(=0)NH-, or -CH₂CH₂NHC(=0)-; Ar is divalent aryl; G is H or methyl;

z is 0 or 1 ;

f is an integer in the range of 0 to 30; and g is 0 or 1 ; with the proviso that when f is 0, g is 0, and when f is in the range of 1 to 30; g is 1 ;

(R¹⁶0)h is polyoxyalkylene, which is a homopolymer, a random copolymer, or a block copolymer of C2-C4-oxyalkylene units, wherein R¹⁶ is C2H4, C3H6, C4H8, or a mixture thereof, and h is an integer in the range of 5 to 250; Y² is -R¹⁶0-, -R¹⁶H-, -C(=0)-, -C(=0)NH-, =R¹⁶NHC(=0)NH-, or -C(=0)NHC(=0)-; and R¹⁷ is substituted or unsubstituted alkyl selected from the group consisting of

C8-C40 linear alkyl, C8-C40 branched alkyl, C8-C40 carbocyclic alkyl, C2-C40 alkyl-substituted, phenyl, aryl-substituted C2-C40 alkyl, and Cs-Cso complex ester; wherein the R17 alkyl group optionally comprises one or more substituents selected from the group consisting of hydroxy, alkoxy, and halogen. and

(E) 0.005 to 5 wt% of a cross linking agent, for introducing branching and

controlling molecular weight, the cross linking monomer comprising polyfunctional units carrying multiple reactive functionalisation groups selected from the group consisting of vinyl, allyl and functional mixtures thereof. Preferably monomer (Surfmer) D has the formula (V)

R¹⁹-C=C-C(O)-O-[R²⁰O]_m-R²¹ (V)

I

_R18

where:

R¹⁸ and R¹⁹ are each independently selected from H, and C1-3 alkyl;

R²⁰ is C2-C4 and mixtures thereof, preferably C2;

m, the average number of alkoxy units R²⁰O, is from 6 to 40;

R²¹ is alkyl or alkylaryl where the alkyl part is linear or branched; and the total number of carbons is from 8 to 40. The liquid detergent composition may optionally include (iv) at least 0.01 wt% suspended particles. Additionally or alternatively, the liquid detergent composition may optionally include (v) at least 2 wt% of a viscosity reducing polymer. In this specification the term (meth)acrylic acid includes both acrylic acid and methacrylic acid and the term (meth)acrylate includes both acrylate and methacrylate.

The viscosity of the liquid at 20 s^"1 and 25°C is preferably at least 0.3 Pa.s, most preferably at least 0.4 Pa.s. This viscosity is also known as the pour viscosity of the composition. The compositions preferably have a yield stress of at least 0.1 Pa to facilitate the preferred suspending properties.

The compositions exhibit suitable pour viscosities while also having a useful rheology for suspending or spraying, despite the inclusion of polymers that have the effect of reducing the pour viscosity of the composition.

When used, the suspended particles may comprise microcapsules and a preferred type of microcapsules is perfume encapsulates. Alternatively or additionally the suspended particles may comprise visual cues. The visual cues may be beads or may comprise lamellar particles formed from sheets of polymer film.

Noteworthy viscosity reducing polymers are ethoxylated polyethylene imine and/or polyester soil release polymer. Preferably polymer (v) comprises at least 3 wt% of ethoxylated polyethylene imine.

In some embodiments copolymer (iii) is formed by addition polymerisation in the presence of: 0.1 to 5 wt% of monomer A; 15 to 60 wt% of monomer B; 30 to 70 wt% of monomer C; 1 to 25 wt% of monomer D and 0.005 to 5 wt.% of cross-linking agent E.

Copolymer (iii) preferably has a molecular weight Mw of at least 500 000, more preferably 1 million Daltons.

It is preferred to use maleic anhydride as the first monomer (A) in the copolymerisation of copolymer (iii). In some embodiments 1 wt.% or less, 0.6 wt.% or less, 0.5 wt.% or less of the first monomer (A) is present in the copolymerisation of copolymer (iii). In further

embodiments, first monomer (A) is present in the copolymerisation of copolymer (iii) in an amount in the range of 0.1 to 1 wt.%, in the range 0.25 to 0.75 wt.%, or in the range of 0.4 to 0.6 wt.%.

The copolymers (iii) are crosslinked alkali swellable hydrophobically modified acrylic copolymers, C-HASE. These polymers require alkaline conditions to swell and so should be added to the composition such that they are exposed to appropriate alkaline

conditions at some stage during the manufacture of the detergent liquid. It is not

essential that the finished liquid composition is alkaline.

Preferably the surfactant system (i) comprises at least 5 wt% total surfactant. In some embodiments, the surfactant system (i) comprises 15 wt.% or more total surfactant.

Preferably the surfactant system (i) comprises at least 3 wt% of anionic surfactant, most preferably the anionic surfactant comprises linear alkyl benzene sulphonate, which is the workhorse surfactant found in most laundry and hand dish wash compositions.

Advantageously the detergent composition comprises an effective amount of at least one enzyme selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase. More advantageously it comprises at least 2 of this group of

enzymes even more advantageously at least 3 and most advantageously at least 4 of the enzymes from this group. The fourth monomer D is more preferably a surfmer of formula (VI):

in which each R¹⁸ and R¹⁹ are independently selected from H, Ci to C3 alkyl, preferably R¹⁸ is a methyl group and R¹⁹ is H; d ranges from 6 to 40 and e ranges from 6 to 40, preferably d ranges from 10 to 30 and e ranges 15 to 35 most preferably d ranges from 12 to 22 and e ranges from 20 to 30. It is preferable that e is greater or equal to d. Preferably the amount of monomer D in copolymer (iv) is in the range of 2 to 15 wt.%, more preferably 3 to 12 wt.% and more preferably 5 to 10 wt. %.

Preferably the level of copolymer (iii) in the detergent composition is from 0.05 to 2 wt% of the total composition; more preferably from 0.1 to 1 wt%.

Detailed Description of the Invention

Polvsurfmer polymer (ii)

The polymer (ii) is formed from the polymerisation of monomers consisting of monomer (A1 ): R¹C=CR²R³ (A1 ) and optionally monomer (A2): R⁴C=CR⁵R⁶ (A2). The polymer is also referred to herein as a "Polysurfmer".

Monomer (A 1)

In some embodiments, R¹ and R² are each independently selected from H and C1-3 alkyl, and R³ has the formula (VII)

-C(0)-0-[R²²0]_r-R²³ (VII)

R²² is C2-C4 and mixtures thereof, preferably C2;

r, the average number of alkoxy units R²²0, is from 6 to 40;

R²³ is alkyl or alkylaryl where the alkyl part is linear or branched; and the total number of carbons is from 8 to 40.

In some embodiments, R¹ and R² are each independently selected from H and C1-3 alkyl, and R³ has the formula (VIII)

-C(0)-0-[C2H₄0]s-CH2-(CH₂)t-CH3 (VIII)

Where s and t are independently in the range of from 6 to 40.

In some embodiments, R¹ is H and R² is a methyl group. In some embodiments, t ranges from 6 to 40 and s ranges from 6 to 40, preferably t ranges from 10 to 30 and s ranges 15 to 35, most preferably t ranges from 12 to 22 and s ranges from 20 to 30. It is preferable that s is greater or equal to t. Monomer (A2)

In some embodiments, R⁴, R⁵ and R¹⁰ are each independently H or methyl. In some embodiments, R⁴ and R¹⁰ are H and R⁵ is methyl.

When monomer (A2) is present in the polymerisation to form polymer (ii), the molar ratio of monomer (A1 ) to monomer (A2) may be in the range of 10:90 to 90:10. In some embodiments, the molar ratio of monomer (A1 ) to monomer (A2) is in the range of 30:70 to 70:30, 40:60 to 40:60 or 45:65 to 65:45.

Degree of polymerisation of polymer (ii)

Polymer (ii) has an average degree of polymerisation of 30 or more. In other words, the polymer has on average 30 or more units of total monomer (A1 ) (and monomer (A2) when present).

In some embodiments, the average degree of polymerisation is in the range of 40 to 200.

Method of polymerisation

The method of poylmerisation of polymer (ii) is not particularly limited. In some embodiments, the polymerisation may be single-electron transfer (SET) polymerisation or free radical polymerisation (FRP). Such polymerisation methods and reagents are known per se.

Optional Copolymer (iii)

The optional copolymers (iii) described herein are crosslinked addition polymers formed by copolymerisation and crosslinking in the presence of three or four different ethylenically unsaturated monomers and a cross-linker. Throughout this specification the monomer ratios are wt% and are based on the amounts of the monomers used. The monomers will lose their unsaturation as they are polymerised and may become salts when neutralised or swollen. Monomer nomenclature and ratios are all made with reference to the unsaturated, and where appropriate unneutralised, starting monomer materials. First Monomer A

The copolymer may be formed in the presence of a monomer A which may ring open to form a diacidic unit in the polymer. Diacidic unit means that carboxylate groups are attached to adjacent carbon atoms in the carbon backbone of the copolymer.

Conveniently this unit is formed from a cyclic ethylenically unsaturated anhydride monomer of formula (II). It is preferred that monomer A is such an anhydride.

O _.

0=C ^ ~ C=0 (II) R^R^{12 X}

where R¹¹ and R¹² are individually selected from H, C1-C3 alkyl, phenyl, chlorine and bromine. Use of a cyclic anhydride monomer with ethylenic unsaturation gives a cis diacid if the ring opens. Such a diacid has both carboxylate groups arranged on the same side of the polymer - but on different carbon atoms.

Preferably R¹¹ is hydrogen and R¹² is selected from the group comprising hydrogen, methyl, bromine and phenyl. More preferably R¹¹ is hydrogen and R¹² is selected from hydrogen and methyl. Most preferably R¹¹ and R¹² are hydrogen so that the anhydride is maleic anhydride. This is the precursor for maleic acid. It is thought that because maleic acid produces carboxylate groups on adjacent carbon atoms in the polymer backbone this increases the localised charge density and causes the difference in performance compared with copolymers not containing this diacid. Itaconic acid which is outside the scope of this invention provides a polymer element where one carbon carries two carboxylate groups and the other carries none. Fumaric acid is the trans isomer of maleic acid it cannot be formed from maleic anhydride monomer by hydrolysis during the emulsion polymerization.

Amounts of Monomer A present in the copolymerisation may range from 0.1 to 5 wt%, preferably from 0.2 to 4 wt%, and more preferably from 0.3 to 1 wt%, and optimally from 0.4 to 0.6 wt% of the total copolymer. Second Monomer B

The second monomer B is a monoacidic vinyl monomer. Suitable monomers are acrylic acid, methacrylic acid, and combinations thereof. In the compositions, the acid groups may be neutralized to form salts. Typical salt counterions to the acid groups are sodium, potassium, ammonium and

triethanolammonium cations.

Amounts of the monoacidic vinyl monomer in the copolymerisation may range from 15 to 60 wt%, preferably from 20 to 55 wt%, more preferably from 25 to 50 wt% of the total monomers.

Third Monomer C

The third monomer, C, includes one or more C-i-Cs esters of acrylic or methacrylic acid. Illustrative ester monomers are ethylacrylate, methylacrylate, ethylmethacrylate, methylmethacrylate, butylacrylate, butylmethacrylate and mixtures thereof. Ethyl acrylate is preferred.

The amount of acrylate ester monomers in the copolymerisation may range from 30 to 70 wt%, preferably from 25 to 60 wt%, and more preferably from 40 to 65 wt% of the total monomers.

Fourth Monomer D

The fourth ethylenically unsaturated monomer, consists of a surfmer of formula (III):

R¹³-C=C-T²-[CH₂]f-[0]_g-[R¹⁶0]h-Y²-R¹⁷ (III)

I

_R14 wherein

R¹³ and R¹⁴ are each independently selected from H, methyl, -C(=0)OH, or -C(=0)OR¹⁵; and R¹⁵ is a C1-C30 alkyl;

T² is -CH₂C(=0)0-, -C(=0)0-, -0-, -CH₂0-, -NHC(=0)NH-, -C(=0)NH-,

-Ar-(CG₂)z-NHC(=0)0-, -Ar-(CG₂)_z-NHC(=0)NH-, or -CH₂CH₂NHC(=0)-;

Ar is divalent aryl; G is H or methyl;

z is 0 or 1 ;

f is an integer in the range of 0 to 30; and g is 0 or 1 ; with the proviso that when f is 0, g is 0, and when f is in the range of 1 to 30; g is 1 ;

(R¹⁶0)_n is polyoxyalkylene, which is a homopolymer, a random copolymer, or a block copolymer of C2-C₄-oxyalkylene units, wherein R¹⁶ is C2H₄, C3H6, CUHs, or a mixture thereof, and n is an integer in the range of 5 to 250;Y² is -R¹⁶0-, -R¹⁶H-, -C(=0)-, - C(=0)NH-, =R¹⁶NHC(=0)NH-, or -C(=0)NHC(=0)-; and

R¹⁷ is substituted or unsubstituted alkyl selected from the group consisting of Cs-C₄o linear alkyl, Cs-C₄o branched alkyl, Cs-C₄o carbocyclic alkyl, C2-C₄o alkyl-substituted, phenyl, aryl-substituted C2-C₄₀ alkyl, and Cs-Cso complex ester; wherein the R¹⁷ group optionally comprises one or more substituents selected from the group consisting of hydroxy, alkoxy, and halogen.

Preferably Surfmer D has the formula (IV)

R¹⁹-C=C-C(O)-O-[R²⁰O]_m-R²¹ (IV)

I

_R18

where:

R¹⁸ and R¹⁹ are each independently selected from H, and C1-3 alkyl;

R²⁰ is C2-C₄ and mixtures thereof, preferably C2;

m, the average number of alkoxy units R²⁰O, is from 6 to 40;

R²¹ is alkyl or alkylaryl where the alkyl part is linear or branched; and the total number of carbons is from 8 to 40.

The fourth monomer D is more preferably a surfmer of formula (V).

in which each R¹⁸ and R¹⁹ are independently selected from H, Ci to Cs alkyl. Preferably R¹⁸ is a methyl group and R¹⁹ is H. d ranges from 6 to 40 and e ranges from 6 to 40, preferably d ranges from 10 to 30 and e ranges 15 to 35 most preferably d ranges from 12 to 22 and e ranges from 20 to 30. It is preferable that d is greater or equal to e. The amount of surfmer D in the copolymer may range from 1 to 25 wt%, preferably from 3 to 20 wt%, and more preferably from 2 to a 12 wt% of the total copolymer.

Cross Linking Agent E

A crosslinking agent, such as a monomer having two or more ethylenic unsaturated groups, is included with the copolymer components during polymerization. Illustrative examples are divinyl benzene, divinyl naphthalene, trivinyl benzene, triallyl

pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaallyl sucrose, trimethylol propane diallyl ether, 1 ,6-hexanediol di(meth) acrylate, tetramethylene tri(meth) acrylate, trimethylol propane tri(meth)acrylate, polyethoxylated glycol di(meth) acrylate, alkylene bisacrylamides, bisphenol A polyethyoxylated dimethacrylate, trimethylolpropane polyethoxylated trimethacrylate, ethylene glycol dimethacrylate and butylene glycol dimethacrylate, diallyl phthalate, allyl methacrylate, diacrylobutylene and similar materials. Preferred for the present invention is bisphenol A polyethoxylated glycol diacrylate, diallyl pentaerythritol and trimethylolpropane triacrylate.

Amounts of the cross linking agent used in the copolymerisation may range from 0.005 to 5 wt%, preferably from 0.05 to 3 wt%, more preferably from 1 to 2 wt%, optimally from 0.2 to 1 wt% of the total monomers. The molecular weight of the copolymer is typically over 1 million.

The copolymer may be prepared in the presence of a chain transfer agent when a crosslinking agent is used. Examples of suitable chain transfer agents are carbon tetrachloride, bromoform, bromotrichloromethane, and compounds having a mercapto group, e.g., long chain alkyl mercaptans and thioesters such as dodecyl-, octyl-, tetradecyl- or hexadecyl-mercaptans or butyl-, isooctyl- or dodecyl-thioglycolates. When used, the amount of chain transfer agent is typically from 0.01 % to 5%, preferably from 0.1 % to 1 %, based on weight of the copolymer components. If the crosslinking agent is used in conjunction with a chain transfer agent, which are conflicting operations for polymerization purposes, not only is exceptional efficiency observed but also very high compatibility with hydrophilic surfactants.

Amount of polymer (ii) and optionally copolymer (iii)

Total amount of polymer (ii) and copolymer (iii) when present in the composition is from 0.05 to 3 wt% of the total composition; more preferably from 0.08 to 2 wt%, even 0.1 to 1 wt%.

In preferred embodiments, copolymer (iii) is present in the composition. In these embodiments, the percentage weight of polymer (ii) may be greater than the weight of monomer D as provided in copolymer (iii) in the composition. For example, polymer (ii) may represent 5 weight percent and monomer D may represent 3 weight percent based on the total weight of polymer (ii) and copolymer (iii) (in other words, copolymer (iii) represents 95 percent by weight of the total weight of polymer (ii) and copolymer (iii)). In some embodiments, the compositions includes polymer (ii) and copolymer (iii) and the weight ratio of polymer (ii) to monomer D in copolymer (iii) in the composition is in the range of 2:1 to 10:1 , 3:1 to 8:1 , or 3.5:1 to 6:1 .

The polymer (and copolymer when present) may be used with other rheology modifiers or thickeners to make up the rheology modified system. Preferred thickeners are thickening polymers and thickening clays.

The polymer (ii) and/or copolymer (iii), in aqueous dispersion or in the dry form, may be blended into an aqueous system to be thickened followed, in the case of a pH-responsive thickener, by a suitable addition of acidic or basic material if required. In the case of pH- responsive thickeners, the pH of the system to be thickened is at, or is adjusted to, at least 5, preferably at least 6, more preferably at least 7; preferably the pH is adjusted to no more than 13. The neutralizing agent is preferably a base such as an amine base or an alkali metal or ammonium hydroxide, most preferably sodium hydroxide, ammonium hydroxide or triethanolamine (TEA). Alternatively, the polymer (ii) and/or copolymer (iii) may first be neutralized in aqueous dispersion and then blended. The surfactant preferably is blended into the aqueous composition separately from the copolymer prior to neutralization. Suspended particles

The composition has a shear thinning rheology that makes it suitable for suspending particles. Thus preferred compositions comprise suspended particles. These particles are preferably solid; that is to say they are neither liquid nor gas. However, within the term solid we include particles with either rigid or deformable solid shells which may then contain fluids. For example the solid particles may be microcapsules such as perfume encapsulates, or care additives or other benefit agents in encapsulated form. The particles may be enzymes or other cleaning actives that are insoluble or are encapsulated to prevent or reduce interaction with other composition ingredients. The particles may take the form of insoluble ingredients such as silicones, quaternary ammonium materials, insoluble polymers, insoluble optical brighteners and other known benefit agents as described, for example, in EP1328616. The amount of suspended particles may be from 0.001 to up to 10 or even 20 wt%. One type of solid particle to be suspended is a visual cue, for example the type of flat film cue described in EP131 19706. The cue may itself contain a segregated component of the detergent composition. Because the cue must be water-soluble, yet insoluble in the composition, it is conveniently made from a modified polyvinyl alcohol that is insoluble in the presence of the mixed surfactant system. In that case, the detergent composition preferably comprises at least 5 wt% anionic surfactant.

The suspended particles can be any type. This includes perfume encapsulates, care encapsulates and/ or visual cues or suspended solid opacifier such as mica or other suspended pearlescent materials and mixtures of these materials. The closer the match of the density of the suspended particles to that of the liquid. Typically, up to 5 wt% of suspended particles may be suspended stably; however, amounts up to 20 wt% are possible.

The benefit agents that may be delivered via suspended particles include any compatible benefit agent which can provide a benefit to a substrate which is treated with a preferably surfactant-containing composition can be used. Advantages of the particles of the invention in the presence of surfactant are a good retention of the benefit agent on storage of a formulation and controllable release of the benefit agent during and after product usage.

Preferred benefit agents are fragrances, profragrance, clays, enzymes, antifoams, fluorescers, bleaching agents and precursors thereof (including photo-bleach), dyes and/or pigments, conditioning agents (for example cationic surfactants including water- insoluble quaternary ammonium materials, fatty alcohols and/or silicones), lubricants (e.g. sugar polyesters), colour and photo-protective agents (including sunscreens),

antioxidants, ceramides, reducing agents, sequestrants, colour care additives (including dye fixing agents), unsaturated oil, emollients, moisturisers, insect repellents and/or pheromones, drape modifiers (e.g. polymer latex particles such as PVAc) and antimicrobial and microbe control agents. Mixtures of two or more of these may be employed. Particular benefit agents are described in further detail below. Benefits include, for laundry applications, benefits of softening, conditioning, lubricating, crease reducing, ease of ironing, moisturising, colour preserving and/or anti-pilling, quick drying, UV protecting, shape retaining, soil releasing, texturising, insect repelling, fungicidal, dyeing and/or fluorescent benefit to the fabric. A highly preferred benefit is the delivery of fragrance (whether free and/or encapsulated), or pro-fragrance or other volatile benefit agent.

Preferred sunscreens are vitamin B3 compounds. Suitable vitamin B3 compounds are selected from niacin, niacinamide, nicotinyl alcohol, or derivatives or salts thereof. Preferred anti-oxidants include vitamin E, retinol, antioxidants based on hydroxytoluene such as Irganox™ or commercially available antioxidants such as the Trollox™ series.

Perfume is one example of a volatile benefit agent. Typical volatile benefit agents have a molecular weight of from 50 to 500. Where pro-fragrances are used the molecular weight will generally be higher.

Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavour Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavour Chemicals by S. Arctander 1969, Montclair, N.J.

(USA). These substances are well known to the person skilled in the art of perfuming, flavouring, and/or aromatizing consumer products, i.e., of imparting an odour and/or a flavour or taste to a consumer product traditionally perfumed or flavoured, or of modifying the odour and/or taste of said consumer product.

By perfume in this context is not only meant a fully formulated product fragrance, but also selected components of that fragrance, particularly those which are prone to loss, such as the so-called 'top notes'. The perfume component could also be in the form of a pro- fragrance. WO 2002/038120 (P&G), for example, relates to photo-labile pro-fragrance conjugates which upon exposure to electromagnetic radiation are capable of releasing a fragrant species.

Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Examples of well-known top-notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Top notes typically comprise 15 to 25 wt% of a perfume composition and in those embodiments of the invention which contain an increased level of top-notes it is envisaged at that least 20 wt% would be present within the encapsulate.

Typical perfume components which it is advantageous to encapsulate include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100 to 250 Celsius. It is also advantageous to encapsulate perfume components which have a low LogP (i.e. those which will be partitioned into water), preferably with a LogP of less than 3.0.

Another group of perfumes with which the present invention can be applied are the so- called 'aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus,

Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian. By means of the present invention these materials can be transferred to textile articles that will be worn or otherwise come into contact with the human body (such as handkerchiefs and bed-linen). The volatile benefit agents also include insect repellent materials (where insect should be read broadly to include other pests which are arthropods but not strictly hexapods - for example ticks). Many of these materials overlap with the class of perfume components and some are odourless to humans or have a non-perfume odour. Commonly used repellents include: DEET (N,N-diethyl-m-toluamide), essential oil of the lemon eucalyptus (Corymbia citriodora) and its active compound p-menthane-3,8-diol (PMD), lcaridin, also known as Picaridin, D-Limonene, Bayrepel, and KBR 3023, Nepetalactone, also known as "catnip oil", Citronella oil, Permethrin, Neem oil and Bog Myrtle. Known insect repellents derived from natural sources include: Achillea alpina, alpha-terpinene, Basil oil (Ocimum basilicum), Callicarpa americana (Beautyberry), Camphor, Carvacrol, Castor oil (Ricinus communis), Catnip oil (Nepeta species), Cedar oil (Cedrus atlantica), Celery extract (Apium graveolens), Cinnamon (Cinnamomum Zeylanicum, leaf oil), Citronella oil (Cymbopogon fleusus), Clove oil (Eugenic caryophyllata), Eucalyptus oil (70%+ eucalyptol, also known as cineol), Fennel oil (Foeniculum vulgare), Garlic Oil (Allium sativum), Geranium oil (also known as Pelargonium graveolens), Lavender oil (Lavandula officinalis), Lemon eucalyptus (Corymbia citriodora) essential oil and its active ingredient p-menthane-3,8-diol (PMD), Lemongrass oil (Cymbopogon flexuosus), Marigolds

(Tagetes species), Marjoram (Tetranychus urticae and Eutetranychus orientalis), Neem oil (Azadirachta indica), Oleic acid, Peppermint (Mentha x piperita), Pennyroyal (Mentha pulegium), Pyrethrum (from Chrysanthemum species, particularly C. cinerariifolium and C. coccineum), Rosemary oil (Rosmarinus officinalis), Spanish Flag Lantana camara (Helopeltis theivora), Solanum villosum berry juice, Tea tree oil (Melaleuca alternifolia) and Thyme (Thymus species) and mixtures thereof. The benefit agent may be encapsulated alone or co-encapsulated with carrier materials, further deposition aids and/or fixatives. Preferred materials to be co-encapsulated in carrier particles with the benefit agent include waxes, paraffins, stabilizers and fixatives.

Silicas, amorphous silicates, crystalline nonlayer silicates, layer silicates, calcium carbonates, calcium/sodium carbonate double salts, sodium carbonates, sodalites, alkali metal phosphates, pectin, carboxyalkylcelluloses, gums, resins, gelatin, gum arabic, porous starches, modified starches, carboxyalkyl starches, cyclodextrins, maltodextrins, synthetic polymers such as polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), cellulose ethers, polystyrene, polyacrylates, polymethacrylates, polyolefins, aminoplast polymers, crosslinkers and mixtures thereof can all provide a basis for benefit agent delivery particles. Polymer particles are however preferred, especially polymer particles which comprise an aminoplast polymer.

Suspension is achieved through providing a yield stress. The yield stress needs to be larger than the stress imposed on the network by the microcapsules or cues otherwise the network is disrupted and the particles can sink or float depending on whether or not they are denser than the base liquid. Perfume microcapsules are almost neutrally buoyant and small, so the required yield stress is low. Air bubbles are bigger and have the biggest density difference and so require a high yield stress (>0.5 Pa, depending on bubble size). If the yield stress is not too high the air bubbles can escape by floating and disengaging from the surface.

Microcapsules preferably comprise a solid shell. Microcapsules carrying an anionic charge should be well dispersed to avoid agglomeration issues. Microcapsules with a cationic charge may also be used. The microcapsule may have a melamine

formaldehyde shell. Other suitable shell material may be selected from (poly)urea, (poly)urethane, starch/ polysaccharide, xyloglucan and aminoplasts.

Delivery aids may be present at the surface of the particle (microcapsule). These can advantageously be selected from non-ionic materials, preferably cellulose derivatives and polyesters, so give better substantivity to a plurality of substrates. Particularly preferred polysaccharide additional deposition aids include dextran, hydroxy-propyl methyl cellulose, hydroxy-ethyl methyl cellulose, hydroxy-propyl guar, hydroxy-ethyl ethyl cellulose, methyl cellulose, locust bean gum, xyloglucan, guar gum. Particularly preferred polyester additional deposition aids include polymers having one or more nonionic hydrophilic components comprising oxyethylene, polyoxyethylene, oxypropylene or polyoxypropylene segments, and, one or more hydrophobic components comprising terephthalate segments. The average particle diameter of the microcapsules lies in the range from 1 to 100 micrometer and at least 90 wt% of the microcapsules preferably has a diameter in this range. More preferably, 90 wt% of the microcapsules have a diameter in the range 2 to 50 micrometers, even more preferably 5 to 50 micrometers. Most preferred are microcapsules with diameters less than 30 micrometers. It is advantageous to have a very narrow particle size distribution, for instance 90 wt% of microcapsules in the range 8 to 1 1 microns. Microcapsules in the range 2 to 5 microns cannot be dispersed so effectively due to the high surface area of the smaller particles.

Preferably the composition comprises at least 0.01 wt% of microcapsules, preferably with an anionic charge. Such microcapsules may deliver a variety of benefit agents by deposition onto substrates such as laundry fabric. To obtain maximum benefit they should be well dispersed through the liquid detergent composition and the vast majority of the microcapsules must not be significantly agglomerated. Any microcapsules that become agglomerated during manufacture of the liquid remain so in the container and will thus be dispensed unevenly during use of the composition. This is highly undesirable. The contents of the microcapsules are normally liquid. For example, fragrances, oils, fabric softening additives and fabric care additives are possible contents. Preferred microcapsules are particles termed core-in-shell microcapsules. As used herein, the term core-in-shell microcapsules refers to encapsulates whereby a shell which is substantially or totally water-insoluble at 40°C surrounds a core which comprises or consists of a benefit agent (which is either liquid or dispersed in a liquid carrier).

Suitable microcapsules are those described in US-A-5 066 419 which have a friable coating, preferably an aminoplast polymer. Preferably, the coating is the reaction product of an amine selected from urea and melamine, or mixtures thereof, and an aldehyde selected from formaldehyde, acetaldehyde, glutaraldehyde or mixtures thereof.

Preferably, the coating is from 1 to 30 wt% of the particles.

Core-in-shell microcapsules of other kinds are also suitable for use in the present invention. Ways of making such other microcapsules of benefit agents such as perfume include precipitation and deposition of polymers at the interface such as in coacervates, as disclosed in GB-A-751 600, US-A-3 341 466 and EP-A-385 534, as well as other polymerisation routes such as interfacial condensation, as described in US-A-3 577 515, US-A-2003/0125222, US-A-6 020 066 and WO-A-03/101606. Microcapsules having polyurea walls are disclosed in US-A-6 797 670 and US-A-6 586 107. Other patent applications specifically relating to use of melamine-formaldehyde core-in-shell microcapsules in aqueous liquids are WO-A-98/28396, WO02/074430, EP-A-1 244 768, US-A-2004/0071746 and US-A-2004/0142868. Perfume encapsulates are a preferred type of microcapsule suitable for use in the present invention.

A preferred class of core-in-shell perfume microcapsule comprises those disclosed in WO 2006/066654 A1 . These comprise a core having from about 5% to about 50 wt% of perfume dispersed in from about 95% to about 50 wt% of a carrier material. This carrier material preferably is a non-polymeric solid fatty alcohol or fatty ester carrier material, or mixtures thereof. Preferably, the esters or alcohols have a molecular weight of from about 100 to about 500 and a melting point from about 37°C to about 80°C, and are substantially water-insoluble. The core comprising the perfume and the carrier material are coated in a substantially water-insoluble coating on their outer surfaces. Similar microcapsules are disclosed in US 5,154,842 and these are also suitable.

The microcapsules may attach to suitable substrates, e.g. to provide persistent fragrance that is desirably released after the cleaning process is complete.

Liquid detergent compositions

The detergent compositions may have a yield stress, also called critical stress, of at least 0.08 Pa, preferably at least 0.09 Pa, more preferably at least 0.1 Pa, even at least 0.15 Pa measured at 25°C. These increasing levels of yield stress are capable of suspending particles of increasingly different density from the bulk liquid. A yield stress of 0.09 Pa has been found sufficient to suspend most types of perfume encapsulates.

The detergent liquid may be formulated as a concentrated detergent liquid for direct application to a substrate, or for application to a substrate following dilution, such as dilution before or during use of the liquid composition by the consumer or in washing apparatus.

Cleaning may be carried out by simply leaving the substrate in contact for a sufficient period of time with a liquid medium constituted by or prepared from the liquid cleaning composition. Preferably, however, the cleaning medium on or containing the substrate is agitated. Product Form

The liquid detergent compositions are preferably concentrated liquid cleaning

compositions. The liquid compositions are pourable liquids. Throughout this specification, all stated viscosities are those measured at a shear rate of 20 s^"1 and at a temperature of 25°C unless stated to be otherwise. This shear rate is the shear rate that is usually exerted on the liquid when poured from a bottle. The liquid detergent compositions according to the invention are shear-thinning liquids. Optional ingredients

The polymer (ii) used in the present invention (as well as the cross linked hydrophobically modified copolymer (iii)) has been found to be compatible with usual ingredients that may be found in detergent liquids. Among which there may be mentioned, by way of example: clays; enzymes, particularly: lipase, cellulase, protease, mannanase, amylase and pectate lyase; cleaning polymers, including ethoxylated polyethylene imines (EPEI) and polyester soil release polymers; chelating agents or sequestrants, including HEDP (1 - Hydroxyethylidene -1 ,1 ,-diphosphonic acid) which is available, for example, as Dequest® 2010 from Thermphos; detergency builders; hydrotropes; neutralising and pH adjusting agents; optical brighteners; antioxidants and other preservatives, including Proxel®; other active ingredients, processing aids, dyes or pigments, carriers, fragrances, suds suppressors or suds boosters, chelating agents, clay soil removal/ anti-redeposition agents, fabric softeners, dye transfer inhibition agents, and transition metal catalyst in a composition substantially devoid of peroxygen species. These and further possible ingredients for inclusion are further described in

WO2009/153184.

Packaging

The compositions may be packaged in any form of container. Their shear thinning properties means that they may be dispensed from a squeezy bottle, from a pump dispenser, from a trigger spray dispenser or by being simply poured from a bottle. The most advantageous form of packing is the type where the product is poured from a bottle, possibly into a measuring cup. The controlled high pour viscosity of the compositions as claimed makes the compositions ideally suited to this mode of dispensing. Typically a plastic bottle with a detachable closure/pouring spout. The bottle may be rigid or deformable. A deformable bottle allows the bottle to be squeezed to aid dispensing. If clear bottles are used they may be formed from PET. Polyethylene or clarified polypropylene may be used. Preferably the container is clear enough that the liquid, with any visual cues therein, is visible from the outside. The bottle may be provided with one or more labels, or with a shrink wrap sleeve which is desirably at least partially transparent, for example 50% of the area of the sleeve is transparent. The adhesive used for any transparent label should not adversely affect the transparency.

The invention will now be further described with reference to the following non-limiting examples and to the drawings of which:

Figure 1 shows a rheology curve for surfactant-containing detergent compositions, some of the compositions including a polysurfmer polymer (ii) of the as described herein. EXAMPLES

Example 1 - Surfmer Synthesis

n = 12

m = 23

Brij® 35P (150 g) Sigma Aldrich was dissolved in 500 ml anhydrous dichloromethane under a nitrogen atmosphere and cooled in an ice bath to 5 °C. Triethylamine (18.6 g) was added via syringe before methacryloyl chloride (20.9 g) was added dropwise over a 30 minute period. After complete addition, the solution was allowed to warm to room temperature and the reaction stirred for 4 weeks. The solution was then filtered to remove the resulting precipitate and washed once with saturated sodium hydrogen carbonate solution (200 ml) and once with saturated brine (200 ml). The solution was then passed through a column containing basic alumina before the product was dried with anhydrous magnesium sulphate, filtered and the solvent removed in vacuo. In subsequent examples the product is referred to as Surfmer A.

Example 2 - Polvsurfmer Synthesis

Monomer stock solution A:

Surfmer A (61w%), methacrylic acid (22w% ), water (12w%) and ethoxylated lauryl alcohol (5w%).

The monomer stock solution was used either as above, or freeze dried to remove water and methacrylic acid to produce solutions with either 0 wt.% or 6.3wt.% methacrylic acid.

Monomer stock solution B:

(C18 example in stock solution) - Cie Surfmer SET method

To a 3-necked round bottom flask fitted with a N2 inlet, thermometer and suba seal fitted with a syringe needle and a magnetic stirrer bar, monomer stock solution A was dissolved in propan-2-ol and water in their required amounts. This solution was then adjusted to pH = 8.6 using ~30wt% NaOH solution. The initiator benzyl-2-bromo-isobutyrate (35587/50) was then added followed by a piece of copper wire. After 30mins degassing, 2,2'- dipyridyl are then added to the reaction flask as the solid. The reaction is stirred overnight at 45°C, taking frequent samples towards the end of the polymerisation for nmr analysis to establish the degree of conversion. 100mg of Cu(l)Br was added after 24 hrs stirring since the conversion didn't seem to be very high. The contents of the flask is then diluted with propan-2-ol, aliquots of ion exchange resin added to remove the copper and the solutions filtered once the polymer solutions appeared free of copper as indicated by the absence of green/blue colour. The IPA/water is removed by rotary evaporation and the resultant polymer stored as received. FRP method

Monomer stock solution B (75g) and a-azo-iso-butyronitrile (0.675g) were dissolved in propan-2-ol (243ml_) and water (19.5ml_) in a 3-necked round bottomed flask fitted with a condenser and large stirrer bar. The solution was sparged with nitrogen for 60 minutes before being heated to 75°C for 20 hours. The resulting polysurfmer was purified by removal of solvent in vacuo and analysed using NMR and GPC. Table 1 - Synthesised polysurfmer polymers

Example 3 - Polysurfmer/copolymer (iii) mixture synthesis

A 3-armed round bottom flask was charged with ethyl acrylate (46.7g), methacrylic acid (27.9g), maleic anhydride (0.39g), Surfmer A (2.55g of stock solution - C12 surfmer (61w%)), polysurfmer 1 (6.04g), methacrylic acid (22w% ) and water (12w%)) and trimethylolpropane triacrylate (0.42g). The mixture was sealed and sparged with nitrogen for 60 minutes before adding and sodium dodecyl sulfonate (SDS) (0.78g) and deoxygenated water (23.75g) and stirring into a pre-emulsion. A multineck round bottom flask was fitted with a nitrogen sparge and overhead stirrer. Deoxygenated water (137g) and SDS (0.23g) were added, stirred at 200 rpm and heated to 90°C. Ammonium persulfate (0.0552g) in water (1 ml) was added via syringe. The pre-emulsion was fed into the reaction solution via peristaltic pump over 120 minutes. After complete addition the a second aliquot of ammonium persulfate (0.0246g) in water (1 ml) was added and the reaction stirred for a further 4hrs. The resulting emulsion was left to cool before being bottled and solids content measured (28.25w%). The amount of surfmer in the total polymer/copolymer mixture is 1 .93 wt. % and the amount of polysurfmer in the total polymer/copolymer mixture is 7.71 wt.%. This provides a surfmer to polysurfmer ratio of 1 :4.

Example 4 - Comparative Polysurfmer/copolymer (iii) mixture synthesis

The synthesis of Example 3 was repeated with a surfmer to polysurfmer ratio of 4:1 .

Example 5 - Alternative HASE Copolymer 1 synthesis (without polysurfmer)

A round bottom flask was charged with ethyl acrylate (EA) (66.19 g), methacrylic acid (MAA)(40.41 g), maleic anhydride (MA) (0.552 g) trimethylolpropane triacrylate (X-linker) (0.576g) and Surfmer A (7.36 g). The mixture was sealed and purged with nitrogen for 60 minutes before sodium dodecyl sulfonate (1 .03 g) and deoxygenated water (26.5 g) was added and stirred forming a pre-emulsion. A multineck round bottom flask was fitted with a nitrogen sparge and overhead stirrer. Deoxygenated water (181 g) and sodium dodecyl sulfonate (0.298 g) were added, stirred at 250 rpm and heated to 90 °C. Ammonium persulfate (0.073 g) in water (1 ml) was added via syringe. The pre-emulsion was fed into the surfactant solution via peristaltic pump over 150 minutes. After complete addition, ammonium persulfate (0.033 g) in water (1 ml) was added and the reaction stirred for a further 240 minutes. The resulting Copolymer 1 and further Copolymers 2 to 4 as shown in Table 1 were synthesised by using suitable adaptations of this process and used as described hereafter.

Table 2

Example 6 - Viscosity measurements

The polysurfmer/copolymer mixture resulting from Examples 3 and 4, and copolymer 4 of Example 5 were added at a level of 1 wt.% to a detergent base, M10, as specified in Table X and the viscosity measured using the following method.

Rheology Flow Curve Measurement

Rheology flow curves are generated using the following three step protocol:- Instrument - Paar Physica - MCR300 with Automatic Sample Changer (ASC)

Geometry - CC27, profiled DIN concentric cylinder Temperature - 25°C Step 1 - Controlled stress steps from 0.01 to 400 Pa; 40 steps logarithmically spaced in stress with 40 s being spent at each point to measure the shear rate (and hence viscosity); Step 1 is terminated once a shear rate of 0.1 s^"1 is reached. Step 2 - Controlled shear rate steps from 0.1 to 1200 s^"1; 40 steps logarithmically spaced in shear rate with 6 seconds being spent at each point to determine the stress required to maintain the shear rate and hence the viscosity.

Step 3 - Controlled shear rate steps from 1200 to 0.1 s^"1; 40 steps logarithmically spaced in shear rate with 6 seconds being spent at each point to determine the stress required to maintain the shear rate and hence the viscosity.

The results of the first two steps are combined being careful to remove any overlap and to ensure that the required shear rates were achieved at the start of the step.

The yield stress in Pa is taken to be the value of the stress at a shear rate of 0.1 s^"1. I.e. the equivalent of the y-axis intercept in a Herschel-Buckley plot of shear stress vs. shear rate. The yield stress was taken as the point at which the data cut the viscosity = 10 Pa.s and the pour viscosity was taken as the viscosity at 20 s^"1, both at 25°C.

Rheoloqy testing

Figure 1 shows the rheology curves of liquid detergent compositions including the polysurfmer/copolymer mixture resulting from Examples 3 and 4, and copolymer 4 of Example 5. The figure shows that only the detergent composition including the polysurfmer/copolymer mixture of Example 3 exhibits an increase in viscosity at a shear stress of 0.1 Pa.

Table 3 - Full Detergent compositions

LAS is linear alkyl benzene sulphonate

SLES is sodium lauryl ether sulphate 3EO

EPEI is ethoxylated polyethylene imine PEI(600) 20EO

MPG is mono propylene glycol

opolymer thickener is polymer(ii) and copolymer mixture of Example 3

Claims

An aqueous detergent liquid composition comprising:

(i) a surfactant system comprising anionic surfactant, and

(ii) at least 0.05 wt % of a polymer formed from the polymerisation of monomers consisting of monomer (A1 ): And optionally monomer (A2):

R⁴C=CR⁵R^b (A2)

Wherein

R¹ and R² are each independently selected from H, methyl, -C(=0)OH, or -C(=0)OR⁷, wherein R⁷ is a C1-C30 alkyl;

R³ is T¹-[R⁸0]_q-Y¹-R⁹ T¹ is -CH₂C(=0)0-, -C(=0)0- or -C(=0)NH-

(R⁸0)_q is polyoxyalkylene, which is a homopolymer, a random copolymer, or a block copolymer of C2-C4-oxyalkylene units, wherein R⁸ is C2H4, C3H6, C4H8, or a mixture thereof, and q is an integer in the range of 5 to 250;

Y¹ is -R⁸0-, -R⁸H-, -C(=0)-, -C(=0)NH-, =R⁸NHC(=0)NH-, or -

C(=0)NHC(=0)-; and

R⁹ is substituted or unsubstituted alkyl selected from the group consisting of C8-C40 linear alkyl, C8-C40 branched alkyl, C8-C40 carbocyclic alkyl, C2-C40 alkyl-substituted, phenyl, aryl-substituted C2-C40 alkyl, and Cs-Cso complex ester;

R⁴ and R⁵ are independently H or Ci-4alkyl, preferably H or methyl;

R⁶ is -C(0)-OR¹⁰, where R¹⁰ is H or Ci_-4 alkyl, preferably H or methyl, more preferably H; and wherein the degree of polymerisation of polymer (ii) is 30 or more.

The aqueous detergent liquid composition according to claim 1 wherein R¹ and R² are each independently selected from H and C1-3 alkyl, and R³ has the formula (VII)

-C(0)-0-[R²²0]_r-R²³ (VII)

R²² is C2-C4 and mixtures thereof, preferably C2;

r, the average number of alkoxy units R²²0, is from 6 to 40;

R²³ is alkyl or alkylaryl where the alkyl part is linear or branched; and the total number of carbons is from 8 to 40, and wherein monomer (I) constitutes at least

26% wt. of the polymer.

The aqueous detergent liquid composition according to claim 2 wherein R¹ and R² are each independently selected from H and C1-3 alkyl, and R³ has the formula (VIII)

-C(0)-0-[C2H₄0]s-CH2-(CH₂)t-CH3 (VIII)

Where s and t are independently in the range of from 6 to 40.

The aqueous detergent liquid composition according to any preceding claim wherein R⁴, R⁵ and R¹⁰ are each independently H or methyl.

The aqueous detergent liquid composition according to any preceding claim further comprising:

(i) at least 0.05 wt% of a suspending system comprising copolymer formed by addition polymerisation in the presence of:

0 to 5 wt% of a first monomer consisting of an ethylenically unsaturated diacid of formula (II):

HOOC-CR¹¹=CR¹²-COOH (II) or an unsaturated cyclic anhydride precursor of such an ethylenically unsaturated diacid, the anhydride having formula (III)

O

0=C ^ ^ 0=0 R^R^{12 X}

where R¹¹ and R¹² are individually selected from H, C1-C3 alkyl, phenyl, chlorine and bromine;

(B) 15 to 60 wt% of a second ethylenically unsaturated monoacidic

monomer consisting of (meth)acrylic acid;

(C) 30 to 70 wt% of a third ethylenically unsaturated monomer consisting of Ci-Cs alkyl ester of (meth)acrylic acid; and

(D) 1 to 25 wt% of a fourth ethylenically unsaturated monomer, consisting of surfmer of formula (IV):

R¹³-C=C-T²-[CH₂]f-[0]_g-[R¹⁶0]h-Y²-R¹⁷ (IV)

I

_R14 wherein each R¹³ and R¹⁴ are each independently selected from H, methyl, - C(=0)OH, or -C(=0)OR¹⁵;

R¹⁵ is a C1-C30 alkyl;

T² is -CH₂C(=0)0-, -C(=0)0-, -0-, -CH2O-, -NHC(=0)NH-, -C(=0)NH-,

-Ar-(CG₂)z-NHC(=0)0-, -Ar-(CG₂)z-NHC(=0)NH-, or -CH₂CH₂NHC(=0)-; Ar is divalent aryl;

G is H or methyl;

z is 0 or 1 ; f is an integer in the range of 0 to 30; and g is 0 or 1 ; with the proviso that when f is 0, g is 0, and when f is in the range of 1 to 30; g is 1 ;

(R¹⁶0)h is polyoxyalkylene, which is a homopolymer, a random copolymer, or a block copolymer of C2-C4-oxyalkylene units, wherein R¹⁶ is C2H4, C3H6, C4H8, or a mixture thereof, and h is an integer in the range of 5 to 250; Y² is -R¹⁶0-, -R¹⁶H-, -C(=0)-, -C(=0)N H-, =R¹⁶N HC(=0)N H-, or -C(=0)N HC(=0)-; and R¹⁷ is substituted or unsubstituted alkyl selected from the group consisting of C8-C40 linear alkyl, C8-C40 branched alkyl, C8-C40 carbocyclic alkyl, C2-C40 alkyl-substituted, phenyl, aryl-substituted C2-C40 alkyl, and Cs-Cso complex ester; wherein the R17 alkyl group optionally comprises one or more substituents selected from the group consisting of hydroxy, alkoxy, and halogen. and

0.005 to 5 wt% of a cross linking agent, for introducing branching and controlling molecular weight, the cross linking monomer comprising polyfunctional units carrying multiple reactive functionalisation groups selected from the group consisting of vinyl, allyl and functional mixtures thereof.

6. A composition according to any preceding claim in which the Surfmer D in

copolymer (iv) has the formula (V):

in which each Re and R9 are independently selected from H , Ci to C3 alkyl;

n ranges from 6 to 40 and m ranges from 6 to 40.

7. A composition according to any preceding claim in which the amount of monomer D in copolymer (iv) is in the range of 2 to 15 wt.%.

8. A composition according to any preceding claim wherein the composition includes 2 wt.% or more of a viscosity reducing polymer (iv) comprising ethoxylated polyethylene imine and/or polyester soil release polymer.

9. A composition according to any preceding claim in which the surfactant system (i) comprises at least 5 wt% total surfactant.

10. A composition according to any preceding claim in which the surfactant system (i) comprises 15 wt.% or more total surfactant.

1 1. A composition according to any preceding claim in which the surfactant system comprises at least 3 wt% anionic surfactant.

12. A composition according to any preceding claim which comprises alkyl benzene sulphonate anionic surfactant.

13. A composition according to claim 1 wherein the viscosity of the liquid at

20 s^"1 and 25°C is at least 0.3 Pa.s, preferably at least 0.4 Pa.s.

14. A composition according to any preceding claim having a yield stress of at least 0.1 Pa.

15. A composition according to claim 14 wherein the suspended particles comprise microcapsules.